Catalytic asymmetric synthesis of homoallylic alcohols: Chiral amplification and chiral poisoning in a titanium/BINOL catalyst system

Journal of the American Chemical Society

Volumn 118, Issue 5, 1996, Pages 1217-1218

  Faller, J W ^a   Sams, D W I ^a   Liu, X ^a  

^a YALE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKANOL;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0029913899     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja952115m     Document Type: Article

References (25)

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5. For example, prices quoted in the Aldrich catalog (1995) are as follows: (R)-BINOL, $219.00 for 5 g; (S)-BINOL, $278.00 for 5 g; and racemic BINOL, $18.90 for 5 g.
6. 1 employs titanium/BINOL systems at 10 mol % (aldehyde to titanium). Since some of the titanium is in the form of reduced activity complexes in our experiments, we employ a higher titanium concentration in these reactions to ensure that the reaction proceeds to completion (see Table 2, entry 1).
7. 254) and 5% acetone in hexanes as eluant.
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10. 11,12
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18. 7 in crystal structures have been quoted as information from Prof. B. Sharpless. A solid state structure could be that of a more insoluble form and may not represent the nature of important oligomers in solution.
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24. In an alternative procedure, the titanium tartrate poison was prepared separately and then added to the titanium catalyst prepared from racemic BINOL. This catalyst also showed chiral poisoning phenomena, but the best results were obtained by preparing the mixture in situ.
25. 5b Excess tartrate could also potentially slow other acid-catalyzed routes that might competitively yield low ee product. We are continuing our efforts to determine the nature of the various complexes in these mixtures.